EP4206182A1 - Ester compound - Google Patents

Ester compound Download PDF

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Publication number
EP4206182A1
EP4206182A1 EP21861653.0A EP21861653A EP4206182A1 EP 4206182 A1 EP4206182 A1 EP 4206182A1 EP 21861653 A EP21861653 A EP 21861653A EP 4206182 A1 EP4206182 A1 EP 4206182A1
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EP
European Patent Office
Prior art keywords
compound
hydrocarbon group
independently
carbon atoms
hetero atom
Prior art date
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EP21861653.0A
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German (de)
English (en)
French (fr)
Inventor
Wataru Yamada
Takaaki Yano
Shotaro Takano
Takashi Kimura
Makoto Isogai
Takashi Nakano
Sunil Krzysztof Moorthi
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Publication of EP4206182A1 publication Critical patent/EP4206182A1/en
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
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    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/64—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring the carbon skeleton being further substituted by singly-bound oxygen atoms
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/28—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with dihydroxylic compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
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    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
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    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/16—Benz[e]indenes; Hydrogenated benz[e]indenes
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/30—Ortho- or ortho- and peri-condensed systems containing three rings containing seven-membered rings
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
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    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
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Definitions

  • the present invention relates to a novel ester compound.
  • a catalyst for olefin polymerization is one of techniques greatly developed up to the present, which was triggered by the discovery of so-called Ziegler-Natta catalysts, for which Ziegler reported in 1953 that ethylene was polymerized even at low pressures by use of a combination of titanium tetrachloride and an organoaluminum compound and Natta subsequently reported the first propylene polymerization by use of a combination of titanium trichloride and a halogen-containing organoaluminum compound.
  • catalysts containing titanium tetrachloride, a magnesium compound, and a Lewis base which are referred to as third generation catalysts, can achieve both high polymerization activity (high productivity) and high stereoregularity in propylene polymerization. This provided one opportunity to allow propylene polymers (polypropylene) to spread around the world.
  • a Lewis base (hereinafter, also referred to as an "internal donor"), one of major components of the above third generation catalyst component (hereinafter, also referred to as a “solid titanium catalyst component”), was found to greatly affect catalyst performance, and various Lewis bases have been developed so far.
  • Patent Literature 1 As Lewis bases for use in Ziegler-Natta catalysts, ethyl benzoate, phthalic esters, 1,3-diketone (Patent Literature 1), malonic ester (Patent Literature 2), succinic ester (Patent Literature 3), 2,4-pentanediol diester (Patent Literature 4), naphthalenediol diester (Patent Literature 5), and catechol diester (Patent Literature 6), for example, have been reported. Mainly enterprises vigorously make research and development in this field even today.
  • Patent Literatures 7 to 11 and Non-Patent Literatures 1 to 19 With respect to elementary reactions for synthesis of various ester compound, a large number of approaches have been disclosed (e.g., Patent Literatures 7 to 11 and Non-Patent Literatures 1 to 19).
  • Propylene polymers while having heat resistance and rigidity similar to those of general-purpose engineering plastics, have an advantage of generating a smaller amount of toxic gas even when combustion-treated, because of being constituted substantially only by carbon and hydrogen.
  • an ester compound having a specific cyclic structure is suitable as a Lewis base for a solid titanium catalyst component, for example, having completed the present invention.
  • the present invention relates to the following [1] to [28], for example.
  • the ester compound of the present invention can be used in resin additives, cosmetics and external preparations for skin, microbicidal compositions, antioxidants, chelators, and Ziegler-Natta catalysts, for example.
  • ester compound (A) is represented by the following general formula (1).
  • R 1 to R 24 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group.
  • R 1 to R 10 , R 23 , and R 24 may be bonded to one another to form a ring or may form a multiple bond at which adjacent substituents are directly bonded.
  • R 11 to R 24 may be bonded to one another to form a ring, or adjacent substituents may be bonded to one another to form a multiple bond.
  • At least one set in R 1 to R 24 is bonded to one another to form a ring structure.
  • n2 to n5 each independently represent an integer of 0 to 2.
  • n1 and n6 each independently represent an integer of 0 or 1.
  • L 1 and L 2 are each independently a hydrocarbon group or a hetero atom-containing hydrocarbon group.
  • any of n4, n5, and n6 is preferably 1 or 2.
  • any of n4, n5, and n6 is preferably 1 or 2.
  • An example of a preferable aspect of the ester compound (A) of the present invention includes compounds represented by the following general formulas (2) to (4).
  • R 1 to R 24 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group
  • R 1 to R 10 , R 23 , and R 24 are optionally bonded to one another to form a ring or optionally form a multiple bond at which adjacent substituents are directly bonded
  • R 11 to R 24 are optionally bonded to one another to form a ring, or adjacent substituents are optionally bonded to one another to form a multiple bond
  • X and Y are each independently a hydrocarbon group, a hetero atom, or a hetero atom-containing hydrocarbon group
  • n2 to n5 each independently represent an integer of 0 to 2
  • n1 and n6 each independently represent an integer of 0 or 1
  • L 1 and L 2 are each independently a hydrocarbon group
  • An example of a more preferable aspect of the ester compound (A) of the present invention also includes compounds represented by the following general formulas (5) to (9). wherein, in the formula (5), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group, R 4 and R 9 are each independently a hydrogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group, R 11 , R 15 , R 17 , and R 21 are each independently a hydrogen atom, a halogen atom, hydrocarbon group, or a hetero atom-containing hydrocarbon group; R 11 , R 15 , R 17 , and R 21 are optionally bonded to one another to form a ring; X is a hydrocarbon group, a hetero atom, or a hetero atom-containing hydrocarbon group; and L 1 and L 2 are each independently a hydrocarbon group or a hetero atom-containing hydrocarbon group having 4 or more carbon atoms.
  • R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group
  • R 4 , R 9 , R 11 , R 12 , R 15 to R 18 , R 21 , and R 22 are each independently a hydrogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group
  • R 11 , R 12 , R 15 to R 18 , R 21 , and R 22 are optionally bonded to one another to form a ring or optionally form a multiple bond at which adjacent substituents are bonded to one another
  • X is a hydrocarbon group, a hetero atom, or a hetero atom-containing hydrocarbon group
  • L 1 and L 2 are each independently a hydrocarbon group or a hetero atom-containing hydrocarbon group having 4 or more carbon atoms.
  • R 4 , R 9 , R 12 , R 15 to R 18 , and R 21 are each independently a hydrogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group; R 15 to R 18 are optionally bonded to one another to form a ring or optionally form a multiple bond at which adjacent substituents are bonded to one another; Y is a hydrocarbon group, a hetero atom, or a hetero atom-containing hydrocarbon group; and L 1 and L 2 are each independently a hydrocarbon group or a hetero atom-containing hydrocarbon group having 4 or more carbon atoms.
  • R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group
  • R 3 , R 4 , R 9 , R 10 , R 12 , R 15 to R 18 , and R 21 are each independently a hydrogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group
  • R 15 to R 18 are optionally bonded to one another to form a ring or optionally form a multiple bond at which adjacent substituents are bonded to one another
  • Y is a hydrocarbon group, a hetero atom, or a hetero atom-containing hydrocarbon group
  • L 1 and L 2 are each independently a hydrocarbon group or a hetero atom-containing hydrocarbon group having 4 or more carbon atoms.
  • R 3 , R 4 , R 9 and R 10 are each independently preferably a substituent selected from a hydrogen atom, a halogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, more preferably selected from a hydrogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, and particularly preferably selected from hydrogen and a hydrocarbon group.
  • hydrocarbon group described above are more specifically substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, and substituted or unsubstituted aryl groups having 6 to 20 carbon atoms.
  • halogen-containing hydrocarbon group described above are substituents in which one or more hydrogen atom in a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms are replaced with a halogen atom.
  • R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group
  • R 4 , R 9 , R 12 , R 15 to R 18 , and R 21 are each independently a hydrogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group
  • R 15 to R 18 are optionally bonded to one another to form a ring or optionally form a multiple bond at which adjacent substituents are bonded to one another
  • X and Y are each independently a hydrocarbon group, a hetero atom, or a hetero atom-containing hydrocarbon group
  • L 1 and L 2 are each independently a hydrocarbon group or a hetero atom-containing hydrocarbon group having 4 or more carbon atoms.
  • ester compounds represented by the formulas (5), (8), and (9) are preferable, compounds represented by the formulas (5) and (9) are more preferable, and ester compounds represented by the formula (5) are most preferable.
  • An example of a preferable aspect of the ester compound (A) of the present invention also includes a compound represented by the following general formula (31).
  • R 1 to R 24 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group.
  • hydrocarbon group can include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.
  • hetero atom-containing hydrocarbon group can include substituted or unsubstituted hetero atom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.
  • hydrocarbon group and the hetero atom-containing hydrocarbon group examples include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, hetero atom-containing alkyl groups, and heteroaryl groups. These groups preferably have 1 to 20 carbon atoms.
  • the lower limit value is preferably 2, more preferably 3, and particularly preferably 4. However, the preferable lower limit value in the case of an aryl group is 6. Meanwhile, the upper limit value is preferably 18, more preferably 15, further preferably 10, and particularly preferably 6.
  • a heteroaryl group preferably has one or more 5 or more-membered ring structures, more preferably has one or more 5 to 7-membered ring structures, and further preferably has one or more 5-membered ring or 6-membered ring structure.
  • At least one substituent of the R 1 to R 24 may be preferably a substituent other than hydrogen. Further, one or more of the carbon atoms forming the cyclic structure may be preferably a quaternary carbon. In an aspect as described above, when the ester compound of the present invention is used as a component of a catalyst for olefin polymerization, the performance balance may be improved.
  • R 1 to R 10 , R 23 , and R 24 may be bonded to one another to form a ring, and R 11 to R 24 may be bonded to one another to form a ring.
  • the moiety forming a ring may be formed with a single bond or may include a double bond.
  • a structure including a carbon-carbon double bond may be preferable.
  • the moiety forming a ring may be preferably a structure further including a ring structure, and an aspect may be preferable in which a double bond, particularly preferably a carbon-carbon double bond is included in the ring structure.
  • Specific examples of the structure of the moiety forming a ring like this are the same as structure examples of X and Y mentioned below.
  • the carbon-carbon double bond includes an aromatic structure.
  • the carbon may be referred to as "B4C"
  • “another substituent” (hereinafter, may be referred to as “B4S”) is usually bonded (e.g., when R 3 is bonded directly to R 10 to form a ring, R 4 and R 9 correspond thereto).
  • the "another substituent” may be preferably a hydrocarbon group and/or a hetero atom-containing hydrocarbon group mentioned below.
  • the hetero atom-containing hydrocarbon group an oxygen-containing hydrocarbon group is particularly preferable.
  • the hydrocarbon group is more specifically an aliphatic group having 1 to 10 carbon atoms, alicyclic group, or aromatic group and more preferably an aliphatic group having 1 to 6 carbon atoms, alicyclic group, or aromatic group.
  • the hetero atom-containing hydrocarbon group is more specifically a hetero atom-containing aliphatic group having 1 to 10 carbon atoms, alicyclic group, or aromatic group and more preferably a hetero atom-containing aliphatic group having 1 to 6 carbon atoms, alicyclic group, or aromatic group.
  • the hetero atom is preferably oxygen.
  • the oxygen-containing hydrocarbon group is further preferably an alkoxy group.
  • the position for such a substituent can include R 4 and/or R 9 in the formulas (2), (4), (5), (6), and (9) and R 12 and/or R 21 in the formulas (3), (4), (7), and (8). More preferable are/is the R 4 and/or R 9 .
  • the substituent at such a position is a group having a structure as above and is used as a component of the catalyst for olefin polymerization, the molecular weight of a polymer to be obtained may be easily controlled via hydrogen, in addition to polymerization activity and stereoregularity.
  • adjacent substituents may be bonded directly to form a multiple bond, for example a double bond or triple bond.
  • an aromatic ring structure in which these substituents are bonded is also within the scope of this invention. Examples thereof can include aromatic ring structures represented by the formulas (5) and (7).
  • substituents forming the ring are selected from substituents other than a hydrogen atom and halogen atoms and are preferably hydrocarbon groups.
  • At least one set in R 1 to R 24 is bonded to one another to form a ring structure.
  • substituents to form the ring of the at least one set are preferably separated by 2 or more carbons and more preferably separated by 3 or more carbons.
  • Such a structure is preferably a ring structure including X or Y in the formulas (2) to (4) and more preferably a ring structure including X or Y in the formulas (5) to (9).
  • substituents selected from R 3 to R 6 , R 7 to R 10 , and R 11 to R 22 are preferably bonded to one another to form the ring.
  • the substituents forming the ring preferably include no carbon atoms in a bridgehead position from the synthetic viewpoint.
  • Carbon atoms in a bridgehead position refer to carbon atoms sharing 2 or more rings.
  • the carbon atom to which X and R 4 are bonded, the carbon atom to which X and R 9 are bonded, the carbon atom to which R 23 is bonded, and the carbon atom to which R 24 is bonded are referred to.
  • Such structures include structures included in the formulas (5) to (9).
  • the structure included in the formula (5) particularly preferable are a structure of a ring formed by bonding of R 11 and R 15 to one another, a structure of a ring formed by bonding of R 15 and R 17 to one another, a structure of a ring formed by bonding of R 17 and R 21 to one another, and a structure composed of these combinations.
  • a structure of a ring formed by bonding of R 11 or R 12 and R 15 or R 16 particularly preferable are a structure of a ring formed by bonding of R 11 or R 12 and R 15 or R 16 , a structure of a ring formed by bonding of R 15 or R 16 and R 17 or R 18 , a structure of a ring formed by bonding of R 17 or R 18 and R 21 or R 22 , and a structure composed of these combinations.
  • a structure of a ring formed by bonding of R 15 or R 16 and R 17 or R 18 is particularly preferable.
  • ester compound (A) having a structure in which R 11 and R 15 are bonded to one another to form a ring in the formula (5) is shown below.
  • ester compound (A) having a structure in which R 15 and R 17 are bonded to one another to form a ring in the formula (5) is shown below.
  • ester compound (A) having a structure in which R 17 and R 21 are bonded to one another to form a ring in the formula (5) is shown below.
  • ester compound (A) having a structure in which R 11 or R 12 is bonded to R 15 or R 16 to form a ring in the formula (6) is shown below.
  • ester compound (A) having a structure in which R 15 or R 16 is bonded to R 17 or R 18 to form a ring in the formula (6) is shown below.
  • ester compound (A) having a structure, in which R 17 or R 18 is bonded to R 21 or R 22 to form a ring in the formula (6), is shown below.
  • ester compound (A) having both a structure in which R 11 or R 12 is bonded to R 15 or R 16 to form a ring and a structure in which R 17 or R 18 is bonded to R 21 or R 22 to form a ring in the formula (6) is shown below.
  • ester compound (A) having a structure in which R 15 or R 16 is bonded to R 17 or R 18 to form a ring in the formula (7) is shown below.
  • ester compound (A) having a structure in which R 15 or R 16 is bonded to R 17 or R 18 to form a ring in the formula (8) is shown below.
  • ester compound (A) having a structure in which R 15 or R 16 is bonded to R 17 or R 18 to form a ring in the formula (9) is shown below.
  • R 15 to R 18 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
  • the R 3 , R 4 , R 9 , and R 10 are each independently preferably a substituent selected from a hydrogen atom, a halogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, more preferably selected from a hydrogen atom, a hydrocarbon group, and a halogen-containing hydrocarbon group, and particularly preferably selected from hydrogen and a hydrocarbon group.
  • hydrocarbon group examples include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, and substituted or unsubstituted aryl groups having 6 to 20 carbon atoms.
  • halogen-containing hydrocarbon group include substituents in which one or more hydrogen atoms in a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms are replaced with a halogen atom.
  • R 1 to R 24 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
  • R 1 to R 24 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.
  • R 1 to R 24 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 10 carbon atoms.
  • R 1 to R 24 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • R 1 , R 2 , R 23 , and R 24 are all hydrogen atoms
  • R 3 to R 22 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • Carbon to which R 1 to R 24 are bonded forms 2 or more ring structures, as shown by the general formula (1).
  • One or more of the ring structures are preferably alicyclic structures. That is, at least not all the rings are preferably aromatic ring structures.
  • R 31 to R 34 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group.
  • hydrocarbon group can include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.
  • hetero atom-containing hydrocarbon group can include substituted or unsubstituted hetero atom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.
  • hydrocarbon group and the hetero atom-containing hydrocarbon group examples include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, hetero atom-containing alkyl groups, and heteroaryl groups. These groups preferably have 1 to 20 carbon atoms.
  • the lower limit value is preferably 2, more preferably 3, and particularly preferably 4. However, the preferable lower limit value in the case of an aryl group is 6. Meanwhile, the upper limit value is preferably 18, more preferably 15, further preferably 10, and particularly preferably 6.
  • a heteroaryl group preferably has one or more 5 or more-membered ring structures, more preferably has one or more 5 to 7-membered ring structures, and further preferably has one or more 5-membered ring or 6-membered ring structure.
  • R 31 to R 34 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
  • R 31 to R 34 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.
  • R 31 to R 34 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 6 carbon atoms.
  • R 31 to R 34 may have a structure of a ring formed by bonding of R 31 to R 34 to one another.
  • R 31 to R 34 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and most preferable R 31 to R 34 are all hydrogen atoms.
  • R 31 to R 34 , R 21 , R 22 , R 4 , and R 9 may be bonded to one another to form a ring, or adjacent substituents may be directly bonded to form a multiple bond.
  • R 31 to R 34 , R 21 , R 22 , R 4 , and R 9 may form a ring in which the substituents are bonded to one another, or adjacent substituents are bonded directly to form a multiple bond, for example, a double bond or triple bond.
  • an aromatic ring structure in which these substituents are bonded is also within the scope of this invention.
  • An example thereof can include an aromatic ring structure in which R 34 , R 21 , and R 22 are bonded.
  • the substituents forming the ring are selected from substituents other than a hydrogen atom and halogen atoms and are preferably hydrocarbon groups.
  • R 31 to R 34 , R 21 , and R 22 are preferably bonded to one another to form a ring, and more preferable is a structure selected from a structure of a ring formed by bonding of R 31 and R 32 to one another, a structure of a ring formed by bonding of R 32 and R 33 to one another, a structure of a ring formed by bonding of R 33 and R 34 to one another, a structure of a ring formed by bonding of R 21 and R 22 to one another, a structure in which R 34 , R 21 , and R 22 are bonded to one another, and combinations thereof.
  • ester compound (A) having a structure in which R 31 and R 32 are bonded to one another to form a ring is shown below.
  • ester compound (A) having a structure in which R 32 and R 33 are bonded to one another to form a ring is shown below.
  • ester compound (A) having a structure in which R 33 and R 34 are bonded to one another to form a ring is shown below.
  • ester compound (A) having a structure in which R 21 and R 22 are bonded to one another to form a ring is shown below.
  • ester compound (A) having a structure in which R 34 , R 21 , and R 22 are bonded to one another to form a ring is shown below.
  • R 21 , R 22 , R 4 , and R 9 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
  • R 21 , R 22 , R 4 , and R 9 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 10 carbon atoms.
  • R 21 , R 22 , R 4 , and R 9 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 6 carbon atoms.
  • R 21 , R 22 , R 4 , and R 9 may have a structure in which R 21 , R 22 , R 4 , and R 9 are bonded to one another to form a ring, and an example thereof may include a ring structure formed by bonding of R 21 and R 22 to one another.
  • R 21 , R 22 , R 4 , and R 9 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and most preferable R 21 , R 22 , R 4 , and R 9 are all hydrogen atoms.
  • L 1 and L 2 are each independently a hydrocarbon group or a hetero atom-containing hydrocarbon group.
  • hydrocarbon group can include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.
  • hetero atom-containing hydrocarbon group can include substituted or unsubstituted hetero atom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.
  • hydrocarbon group and the hetero atom-containing hydrocarbon group examples include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, hetero atom-containing alkyl groups, and heteroaryl groups. These groups preferably have 1 to 20 carbon atoms.
  • the lower limit value is preferably 2, more preferably 3, and particularly preferably 4. However, the preferable lower limit value in the case of an aryl group is 6. Meanwhile, the upper limit value is preferably 18, more preferably 15, further preferably 10, and particularly preferably 6.
  • a heteroaryl group preferably has one or more 5 or more-membered ring structures, more preferably has one or more 5 to 7-membered ring structures, and further preferably has one or more 5-membered ring or 6-membered ring structure.
  • the preferable number of carbon atoms described above is selected from in the range of 4 or more or of 1 to 20. In the latter case, the number is more preferably from 1 to 10. In the former case, the number is more preferably from 4 to 20.
  • L 1 and L 2 in the former are each independently a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 4 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 4 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms.
  • L 1 and L 2 are each independently a substituted or unsubstituted alkyl group having 4 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted hetero atom-containing alkyl group having 4 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 15 carbon atoms.
  • L 1 and L 2 are each independently a substituted or unsubstituted aryl group having 6 to 10 carbon atoms and a substituted or unsubstituted heteroaryl group having 4 to 10 carbon atoms, and particularly preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
  • aryl groups containing a substituent other than hydrogen are hydrocarbon groups having 1 to 10 carbon atoms and hetero atom-containing hydrocarbon groups having 1 to 10 carbon atoms.
  • the hetero atom is specifically an element of Group 16 of the periodic table and more specifically oxygen.
  • hydrocarbon group can include a methyl group, an ethyl group, an isopropyl group, a n-butyl group, a s-butyl group, and a t-butyl group
  • hetero atom-containing hydrocarbon group can include a methoxy group, an ethoxy group, an isopropoxy group, a n-butoxy group, a s-butoxy group, and a t-butoxy group, as preferable examples.
  • n2 to n5 represent integers of 0 to 2
  • n1 and n6 represent integers of 0 or 1.
  • X and Y are each independently a hydrocarbon group, a hetero atom, or a hetero atom-containing hydrocarbon group and preferably each independently a divalent group selected from the groups shown in the following general formula group (10).
  • R 1 ' to R 7 ' are each independently a hydrogen atom, a hydrocarbon group, or a hetero atom-containing hydrocarbon group, and R 2 ' to R 7 ' are optionally bonded to one another to form a ring, or adjacent substituents are optionally directly bonded to form a multiple bond.
  • R 1 ' to R 7 ' are each independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted hetero atom-containing hydrocarbon group having 1 to 10 carbon atoms.
  • R 1' to R 7' are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, and most preferable R 1 ' to R 7 ' are all hydrogen atoms.
  • R 2 ' to R 7 ' may be bonded to one another to form a monocyclic ring or a polycyclic ring.
  • R 1' to R 7' can be bonded with the R 1 to R 24 to form a ring structure.
  • X and Y are preferably divalent groups selected from the groups shown in the following general formula group (11). wherein, in the group (11), R 1' to R 5' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hetero atom-containing hydrocarbon group having 1 to 20 carbon atoms, and R 2' to R 5' are optionally bonded to one another to form a ring, or adjacent substituents are optionally directly bonded to form a multiple bond.
  • R 1' to R 5' are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • X and Y are further preferably divalent groups selected from the groups shown in the following general formula group (12) .
  • R 2' to R 5' are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hetero atom-containing hydrocarbon group having 1 to 20 carbon atoms, and R 2' to R 5' may be bonded to one another to form a ring.
  • X and Y are particularly preferably divalent groups shown in the following general formula (13).
  • R 2' and R 3' are each independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hetero atom-containing hydrocarbon group having 1 to 20 carbon atoms, and R 2' and R 3' may be bonded to one another to form a ring.
  • R 2' and R 3' are preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and more preferably both are hydrogen atoms.
  • R 2 ' to R 7 ' may be preferably bonded to one another to further form a ring, or adjacent substituents may be preferably directly bonded to form a multiple bond.
  • a carbon-carbon double bond is preferable.
  • the moiety further forming a ring by bonding of the R 2' to R 7' to one another preferably has a structure including a carbon-carbon double bond.
  • R 2' to R 5' are preferably bonded to one another to form a ring, and more preferably, a substituted or unsubstituted aryl group is included in the multiple bond.
  • An example of the substituent of such X and Y is shown below.
  • hydrocarbon group can include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted aryl groups.
  • hetero atom-containing hydrocarbon group can include substituted or unsubstituted hetero atom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.
  • hydrocarbon group and the hetero atom-containing hydrocarbon group examples include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, hetero atom-containing alkyl groups, and heteroaryl groups. These groups preferably have 1 to 20 carbon atoms.
  • the lower limit value is preferably 2, more preferably 3, and particularly preferably 4. However, in the case of an aryl group, the preferable lower limit value is 6, and the upper limit value is preferably 20, more preferably 15, further preferably 10, and particularly preferably 6.
  • a heteroaryl group preferably has one or more 5 or more-membered ring structures, more preferably has one or more 5 to 7-membered ring structures, and further preferably has one or more 5-membered ring or 6-membered ring structure.
  • R 1 to R 24 More specific examples of the groups and atoms exemplified for R 1 to R 24 , R 31 to R 34 , L 1 , L 2 , and R 1' to R 7' are shown hereinafter.
  • halogen atom examples include fluorine, chlorine, bromine, and iodine.
  • hydrocarbon group various structures can be exemplified such as aliphatic, branched aliphatic, alicyclic, and aromatic structures as described below.
  • Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a n-hexyl group, a thexyl group, a cumyl group, and a trityl group.
  • Examples of the substituted or unsubstituted alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group.
  • Examples of the substituted or unsubstituted alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group.
  • Examples of the substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a cyclopentadienyl group, an indenyl group, and a fluorenyl group.
  • Examples of the substituted or unsubstituted aryl group include aromatic hydrocarbon groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a diisopropylphenyl group, a dimethylisopropylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group and hetero atom-substituted aryl groups such as a methoxyphenyl group, a dimethylaminophenyl group, a nitrophenyl group, and a trifluoromethylphenyl group.
  • aromatic hydrocarbon groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a diisopropylphenyl
  • Examples of the substituted or unsubstituted hetero atom-containing hydrocarbon group include hetero atom-containing alkyl groups such as a methoxymethyl group, a methoxyethyl group, a benzyloxy group, an ethoxymethyl group, and an ethoxyethyl group, and heteroaryl groups such as a furyl group, a pyrrolyl group, a thienyl group, a pyrazolyl group, a pyridyl group, a carbazolyl group, an imidazolyl group, a dimethylfuryl group, a N-methylpyrrolyl group, a N-phenylpyrrolyl group, a diphenylpyrrolyl group, a thiazolyl group, a quinolyl group, a benzofuryl group, a triazolyl group, and a tetrazolyl group.
  • hetero atom-containing alkyl groups such as a meth
  • the number of carbon atoms contained in a substituent containing carbon as described above is, as previously described, preferably from 1 to 20, more preferably from 1 to 10, further preferably from 1 to 6, and particularly preferably from 1 to 4.
  • the number of carbon atoms when the substituent has an aryl group structure is preferably from 4 to 20, more preferably from 4 to 10, and further preferably from 6 to 10.
  • R 1 to R 24 when being substituents other than a hydrogen atom, are preferably selected from the hydrocarbon groups and oxygen-containing hydrocarbon substituents described above.
  • the oxygen-containing hydrocarbon group an alkoxy group is further preferable.
  • ester compound (A) of the present invention is not limited thereto.
  • Examples of a compound of which the moiety forming a ring by bonding of R 1 to R 24 has a structure having a ring structure further including a double bond or a ring structure, particularly a double bond can include compounds of the following structures.
  • a methyl group is denoted as “Me”
  • an ethyl group is denoted as “Et”
  • a propyl group is denoted as “Pr”
  • a butyl group is denoted as “Bu”
  • a phenyl group is denoted as "Ph”
  • [n] represents "normal”
  • [i] represents “iso”
  • t represents "tertially”.
  • the OCOL 1 group and OCOL 2 group bonded to the alicyclic structure may form a cis structure or a trans structure derived from the alicyclic structure, and the ester compound of the cis structure is preferably the main component.
  • the main component here refers to the content of the compound of the cis structure exceeding 50 mol% and preferably the content being 70 mol% or more.
  • ester compound (A) of the present invention is suitable as a Lewis base (internal donor) component of the solid titanium catalyst component
  • the present inventors presume the reason as follows.
  • the ester compound (A) of the present invention has a structure in which rings are connected and preferably also has a crosslinked structure (structure corresponding to the X or Y described above). This requirement restricts the conformation of the compound, and that fixes the distance between the two adjacent ester groups bonded to the rings and the orientation of the ester groups. Consequently, when the ester is coordinated to magnesium chloride, the coordination mode for the ester is limited, and a rigid polymerization environment including titanium atoms, magnesium chloride, and the ester compound is presumably formed. When the polymerization proceeds under the environment, it is conceived that the orientation of the polymer chain and the insert direction of propylene are highly regulated to thereby form a catalyst suitable for high stereoregular polymerization.
  • a skeleton in which the ester is bonded to a ring including a crosslinked structure (e.g., the formulas (5), (6), and (9)) is subjected to a restriction on the distance and the orientation of the ester moieties, and thus is a more excellent skeleton as the internal donor for a Ziegler catalyst.
  • a skeleton in which the ester moieties are directly bonded to the cyclohexane skeleton e.g., the formula (8)
  • it is conceived that fusing a ring structure including a crosslinked structure to the cyclohexane skeleton causes the conformation of the cyclohexane skeleton to be restricted and a similar effect is consequently achieved.
  • the ester compound (A) of the present invention which has a structure in which rings are connected as described above, is presumed to have moderate rigidity as a compound and a relatively smaller displacement of the structure. For this reason, in the case of use in a catalyst for olefin polymerization mentioned below, it is expected that a stable structure is kept while a moderate interaction is provided when the ester group-containing compound (A) is coordinated to a titanium compound or magnesium compound. Therefore, it is conceived that the stereospecificity and activity are positively influenced by the interaction. Meanwhile, an alicyclic structure as described above will exhibit various structures liable to be displaced in respect of a local structure, such as a chair type or a boat type. Accordingly, a polymer having a broad molecular weight distribution can be expected to be produced.
  • the ester compound (A) of the present invention represented by the formula (31) has a particular multicyclic structure as described above.
  • the compound also has a specific asymmetric structure. Having such a structure allows the compound to have moderate rigidity.
  • active species for olefin polymerization are formed by an interaction with a magnesium compound or titanium compound and polymerization reaction occurs, there is conceived to be a possibility of fewer displacements or fluctuations as for the structures.
  • an ester compound (A) having an asymmetric structure as that of the formula (31) there may be more conformations in the case of an interaction with a magnesium compound or titanium compound than those of a symmetric compound.
  • the compound preferably has a specific asymmetric structure including an aryl structure, the compound may have enabled a robust coordination structure to be achieved with the magnesium compound or titanium compound.
  • ester compound (A) of the present invention is presumably suitable as a Lewis base (internal donor) component of the solid titanium catalyst component.
  • the method for producing the ester compound (A) of the present invention is not particularly limited.
  • the ester compound (A) can be obtained by the reaction of a dihydroxylation of a corresponding olefin, followed by an esterification of the diol obtained by the dihydroxylation.
  • the ester compound (A) can be also obtained by the successive reaction of introducing a carbonate group to a particular polycyclic compound such as anthracene, a hydrolysis of the carbonate group, and then an esterification of the diol obtained by the hydrolysis. More specifically, the ester compound (A) can be produced as follows.
  • the olefin shown in the following formula (21) can be synthesized by a Diels-Alder reaction of cyclopentadiene and norbornene, for example (Non-Patent Literature 1).
  • the olefin shown in the following general formula (33) can be synthesized by a Diels-Alder reaction of a substituted indene and a substituted diene (Patent Literature 11).
  • a dimer of a diene e.g., dicyclopentadiene
  • dicyclopentadiene which is a precursor
  • the product obtained by the Diels-Alder reaction is often a mixture of an endo form and an exo form (see the following formulas (22) and (34)), but either of the isomers can be applied to the present invention. That is, any of the mixture, only the endo form, or only the exo form may be applied. These endo form structure and exo form structure are often reflected also on the structure of the ester compound as a final product.
  • Non-Patent Literatures 2, 3, and 14 A cyclic olefin can be obtained by decarbonylating and decarboxylating an alicyclic dicarboxylic anhydride in the presence of a nickel complex (e.g., tetrakis triphenylphosphine nickel) with a reagent that can function as a ligand (e.g., triphenylphosphine) to the nickel complex (Patent Literatures 7 and 8).
  • a nickel complex e.g., tetrakis triphenylphosphine nickel
  • a reagent that can function as a ligand e.g., triphenylphosphine
  • the compound can be synthesized by subjecting anthracene to a Diels-Alder reaction with vinylene carbonate to give a carbonate compound, and then subjecting the carbonate compound to a hydrolysis, followed by an esterification of the diol.
  • Anthracene can be synthesized, for example, by reacting anthraquinone with an organometallic reagent (e.g., an alkyl lithium or Grignard reagent) and then conducting reduction (e.g., a reaction using tin(II) chloride or sodium hypophosphite) (the following formula (14(1)), see Patent Literature 9 and Non-Patent Literatures 15 and 16).
  • organometallic reagent e.g., an alkyl lithium or Grignard reagent
  • reduction e.g., a reaction using tin(II) chloride or sodium hypophosphite
  • Anthracene can be synthesized also by subjecting a dihalogenoanthracene to a displacement reaction by a metal reagent (e.g., lithium or magnesium) and a halogenated alkyl and to a coupling reaction using a transition metal catalyst (e.g., nickel or palladium) and an organometallic reagent (e.g., a boronic ester or Grignard reagent) (the formulas (14(2)) and (14(3)), see Patent Literature 10 and Non-Patent Literature 17).
  • a metal reagent e.g., lithium or magnesium
  • a halogenated alkyl e.g., a halogenated alkyl
  • a transition metal catalyst e.g., nickel or palladium
  • an organometallic reagent e.g., a boronic ester or Grignard reagent
  • a dialkoxy anthracene can be obtained by reacting anthraquinone with a reducing agent (e.g., zinc) and an electrophile (e.g., a halogenated alkyl or sulfonic ester) (the formula (14(4)), see Non-Patent Literature 18).
  • a reducing agent e.g., zinc
  • an electrophile e.g., a halogenated alkyl or sulfonic ester
  • R 25 M represents an organometallic reagent
  • R 25 represents an alkyl group
  • M represents a metal or metal halide.
  • An example of M includes Li, MgBr, MgCl, and MgI.
  • R 26 Z represents an electrophile
  • Z represents a halogen atom
  • R 26 represents an alkyl group.
  • Z represents a halogen atom
  • R 27 represents an alkyl group or aryl group
  • a and A' represents a hydroxyl group or a crosslinked structure in which A and A' are bonded.
  • An example of the structural formula of a boric acid compound and a boric ester (preferably a cyclic boric ester compound), which are boron-containing compounds including the structures of the above R 27 , A, and A', can include structures represented by the following formula groups (15).
  • R 28 Z represents an electrophile
  • Z represents a halogen atom
  • R 28 represents an alkyl group.
  • Diol forms (the formula (23) and the formula (35)), which are precursors of the ester, can be produced with corresponding olefins (the formula (21) and the formula (33)) as the raw material.
  • olefins the formula (21) and the formula (33)
  • a reaction of an olefin with potassium permanganate (Non-Patent Literature 4) or osmium tetroxide (Non-Patent Literature 5) enables a diol form (the formula (23) and the formula (35)) to be obtained directly.
  • diol forms (the formula (23) and the formula (35)) can be obtained by epoxidizing the olefin moiety using m-chloroperoxybenzoic acid (Non-Patent Literature 6);tert-butyl peroxide (Non-Patent Literature 7); dimethyldioxirane (Non-Patent Literature 8); formic acid and hydrogen peroxide solution (Non-Patent Literature 9); hydrogen peroxide solution and a molybdenum catalyst; or hydrogen peroxide solution and a tungsten catalyst (Non-Patent Literature 10) followed by an acidic or alkali hydrolysis reaction.
  • a diol compound can also be obtained after a hydrolysis of the cyclic carbonate that is obtained from the aforementioned diene or anthracene compound. The details are as follows.
  • the cyclic carbonate (the formula (24)), which is a precursor of the diol form (the formula (23)), can be produced by a Diels-Alder reaction of a corresponding diene and vinylene carbonate (Non-Patent Literature 19).
  • a dimer of the diene which is a precursor, also can be used as the raw material.
  • the product obtained by the Diels-Alder reaction is often a mixture of an endo form and an exo form, and even the present Diels-Alder isomer can be applied.
  • a polycyclic carbonate of a particular structure as shown in examples mentioned below can be obtained by using a polycyclic aromatic compound such as anthracene instead of the diene.
  • An ester form corresponding to the formula (1) can be synthesized by allowing the diol form (the formula (23)) and an acid chloride to react in the presence of a base (the formula 25).
  • a base examples include, but are not particularly limited to, sodium hydroxide, potassium hydroxide, and amine bases.
  • the ester form can be synthesized also by a synthesis method in which the diol form and a carboxylic acid are allowed to react in the presence of an acid catalyst or by using a condensing agent such as DCC (Non-Patent Literature 11) (the formula (26)).
  • an isomer corresponding to the formula (24) may be formed, but subsequently allowing an acid chloride or carboxylic acid to react enables a compound corresponding to the formula (1) to be obtained.
  • L 1 and L 2 may be the same or different.
  • the ester form can be synthesized also by allowing the diol form to react with a carboxylic acid in the presence of an azocarboxylic ester and triphenylphosphine (Non-Patent Literature 12).
  • An ester form corresponding to the formula (31) can be synthesized by allowing the diol form (the formula (35)) and an acid chloride in the presence of a base, as shown in the following formula (37).
  • a base examples include, but are not particularly limited to, sodium hydroxide, potassium hydroxide, and amine bases.
  • the ester form can be synthesized also by a synthesis method in which the diol form and a carboxylic acid are allowed to react in the presence of an acid catalyst or by using a condensing agent such as DCC (Non-Patent Literature 11) (see the formula (38)).
  • an isomer corresponding to the formula (36) may be formed, but subsequently allowing an acid chloride or carboxylic acid to react enables a compound corresponding to the formula (31) to be obtained.
  • L 1 and L 2 may be the same or different.
  • the ester form can be synthesized also by allowing the diol form to react with a carboxylic acid in the presence of an azocarboxylic ester and triphenylphosphine (Non-Patent Literature 12).
  • the ester compound may be obtained as a mixture of an endo form and an exo form, as described previously. From the structural viewpoint, the endo form tends to be easily produced.
  • the isomer ratio when the compound is obtained as a mixture of these is not particularly limited, and a preferable example can include an endo form/exo form ratio of 100/0 to 50/50, preferably of 95/5 to 60/40, and further preferably of 90/10 to 65/35.
  • endo form and exo form often can be separated by a known column chromatography using silica gel.
  • the isomer ratio can be changed also by an isomerization reaction using a solid acid catalyst such as zeolite. It is certainly possible to adjust a desired isomer ratio by combining each of the compounds isolated at a specific ratio.
  • a solid acid catalyst such as zeolite.
  • it is expected that either of the endo form and exo form may exhibit a suitable effect or that a suitable effect may be exhibited at a specific isomer ratio. In such cases, it is only required to adjust the isomer ratio within 100/0 to 0/100 by a method as described above, for example, before use.
  • ester compound (A) of the present invention each of the endo form and the exo form may be used singly or an isomer mixture may be used in various applications, as described above.
  • the ester compound (A) of the present invention is suitable as the Lewis base component of the solid titanium catalyst component, as mentioned previously, but is not limited to this application. It is needless to say that the ester compound has a possibility to be applied in known additive applications such as additives to various resins, cosmetics and external preparations for skin, microbicidal compositions, antioxidants, and chelators.
  • a method for synthesizing the ester compound of the present invention will be exemplified in the following Examples.
  • Compounds of structural formulas disclosed in the following Examples and Comparative Examples represent the structures of the main component of stereoisomers and may include other stereoisomers.
  • the main component refers to a component exceeding 50 mol%, preferably of 70 mol% or more.
  • the peak temperature considered to be the melting point was observed.
  • the temperature at which heat absorption was finished was defined as the melting completion temperature.
  • the isomers were separated by a conventional silica column chromatography. From the results of the NMR analysis of the isolated isomers and the NMR analysis of the mixture, the chemical shifts specific to the isomers were identified, and the isomer ratio was identified with the absorption intensity ratio thereof.
  • the hydrogen of the tetramethylsilane was set to 0 ppm. Peaks of 1 H derived from an organic acid compound, for example, were assigned by a conventional method.
  • a compound 1 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 2 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 10.37 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 6.67 g (16.6 mmol, white solid) of the compound 2.
  • the 1 H-NMR data of the compound 2 obtained are shown below.
  • the melting completion temperature of the compound 2 obtained was 141°C.
  • a compound 3 shown below was synthesized by a method mentioned below.
  • a compound 4 shown below was synthesized by a method mentioned below.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 11.3 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 4.44 g (11.0 mmol, white solid) of the compound 4.
  • the 1 H-NMR data of the compound 4 obtained are shown below.
  • the melting completion temperature of the compound 4 obtained was 163°C.
  • a compound 5 shown below was synthesized by a method mentioned below.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed.
  • the precipitate formed was removed by filtration, and the filtrate was extracted with ethyl acetate 3 times.
  • the organic layer was washed with brine and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 8.19 g of the compound 5.
  • the 1 H-NMR data of the compound 5 obtained are shown below.
  • a compound 6 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 6 obtained was 139°C.
  • a compound 7 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 8 shown below was synthesized by a method mentioned below.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed.
  • the precipitate formed was removed by filtration, and the filtrate was extracted with ethyl acetate 3 times.
  • the organic layer was washed with brine and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 3.03 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 2.02 g (10.7 mmol) of the compound 8.
  • the 1 H-NMR data of the compound 8 obtained are shown below.
  • a compound 9 shown below was synthesized by a method mentioned below.
  • the magnesium sulfate was filtered, and the filtrate was concentrated in a rotary evaporator to thereby give 4.78 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 3.29 g (7.9 mmol, white solid) of the compound 9.
  • the 1 H-NMR data of the compound 9 obtained are shown below.
  • the melting completion temperature of the compound 9 obtained was 196°C.
  • a compound 10 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 11 shown below was synthesized by a method mentioned below.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed.
  • the precipitate formed was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times.
  • the organic layer was washed with brine and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 3.80 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 3.04 g (16.0 mmol) of the compound 11.
  • the 1 H-NMR data of the compound 11 obtained are shown below.
  • a compound 12 shown below was synthesized by a method mentioned below.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 7.91 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 4.82 g (12.1 mmol, white solid) of the compound 12.
  • the 1 H-NMR data of the compound 12 obtained are shown below.
  • the melting completion temperature of the compound 12 obtained was 155°C.
  • a compound 13 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the organic layer was washed twice with 0.5 N hydrochloric acid, twice with water, and once with brine, and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was distilled, and the component at 664 to 665 torr and the distillation temperatures of 88 to 92°C was collected to give 18.09 g of the compound 13.
  • a compound 14 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 14-2 shown below was synthesized by a method mentioned below.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed.
  • the precipitate formed was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times.
  • the organic layer was washed with brine and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 5.63 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 3.85 g (19.0 mmol) of the compound 14-2.
  • the 1 H-NMR data of the compound 14-2 obtained are shown below.
  • a compound 15 shown below was synthesized by a method mentioned below.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 9.65 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 3.88 g (9.5 mmol, white solid) of the compound 15.
  • the 1 H-NMR data of the compound 15 obtained are shown below.
  • the melting completion temperature of the compound 15 obtained was 111°C.
  • a compound 16 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 17 shown below was synthesized by a method mentioned below.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed.
  • the precipitate formed was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times.
  • the organic layer was washed with brine and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator.
  • the crude product was purified by silica gel column chromatography to give 4.11 g (17.7 mmol) of the compound 17.
  • the 1 H-NMR data of the compound 17 obtained are shown below.
  • a compound 18 shown below was synthesized by a method mentioned below.
  • the organic layer was washed with water 3 times and once each with a saturated ammonium chloride aqueous solution and brine in the order mentioned, and dried over magnesium sulfate.
  • the magnesium sulfate was filtered, and the filtrate was concentrated in a rotary evaporator to thereby give 9.34 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 6.13 g of a solid component.
  • the obtained solid was recrystallized with hexane to give 4.0 g (9.0 mmol, white solid) of the compound 18.
  • the 1 H-NMR data of the compound 18 obtained are shown below.
  • the melting completion temperature of the compound 18 obtained was 115°C.
  • a compound 19 shown below was synthesized by a method mentioned below.
  • a compound 20 shown below was synthesized by a method mentioned below.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the reaction solution until a white precipitate formed.
  • the precipitate formed was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times.
  • the organic layer was washed with brine and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator.
  • the crude product was purified by silica gel column chromatography to give 2.25 g (11.0 mmol) of the compound 20.
  • the 1 H-NMR data of the compound 20 obtained are shown below.
  • a compound 21 shown below was synthesized by a method mentioned below.
  • the organic layer was washed with water 3 times, once each with a saturated ammonium chloride aqueous solution and brine in the order mentioned, and dried over magnesium sulfate.
  • the magnesium sulfate was filtered, and the filtrate was concentrated in a rotary evaporator to thereby give 4.82 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 4.44 g (10.8 mmol, pale yellow solid) of a compound 21.
  • the 1 H-NMR data of the compound 21 obtained are shown below.
  • the melting completion temperature of the compound 21 obtained was 152°C.
  • a compound 22 shown below was synthesized by a method mentioned below.
  • a 1 L 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 6.00 mL (44.1 mmol, 1 equivalent) of 2-isopropyl phenol was loaded followed by addition of 100 mL of dichloromethane and 0.62 mL (4.41 mmol, 0.1 equivalents) of diisopropylamine.
  • N-bromosuccinimide N-bromosuccinimide (NBS) dissolved in 400 mL of dichloromethane was slowly added dropwise to the reaction solution prepared previously under room temperature conditions, and the reaction solution after the dropwise addition finished was stirred for an hour at room temperature. After the reaction finished, hydrochloric acid (2 M) was added until the pH reached 1, and after addition of 100 mL of water, extraction was conducted with dichloromethane 3 times. The gathered organic layer was dried over sodium sulfate and then concentrated in a rotary evaporator.
  • NPS N-bromosuccinimide
  • the resultant crude product was purified by silica gel column chromatography (eluent: hexane) to result in 9.40 g (43.7 mmol, yield 910) of the compound 22.
  • the obtained compound exhibited a good agreement with the spectrum of the identical compound synthesized in " J. Med. Chem. 2017, 60, 3618-3625 ".
  • the 1 H-NMR data of the compound 22 obtained are shown below.
  • a compound 23 shown below was synthesized by a method mentioned below.
  • a 500 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a reflux condenser, a flat plug, and a three-way cock.
  • 9.40 g (43.7 mmol, 1 equivalent) of the compound 22, 85 mL of THF, and 12.0 mL (56.8 mmol, 1.3 equivalents) of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) were added thereto, the flat plug was replaced with a thermometer, followed by stirring under heating in an oil bath at 80°C. After stirring overnight followed by allowing to cool to room temperature, the pressure was reduced under a nitrogen atmosphere, and THF and unreacted HMDS were removed from the reaction system. The product in this reaction was not purified and used as was in the following reaction.
  • the container including the product of the reaction described above was equipped with a dropping funnel and, after addition of 120 mL of THF, cooled to -78°C. 38.3 mL (1.6 M, 61.2 mmol, 1.4 equivalents) of a solution of n-BuLi in hexane was slowly added dropwise, and after the dropwise addition finished, stirring was conducted at -78°C for 30 minutes. Subsequently, 10.0 mL (61.0 mmol, 1.4 equivalents) of trifluoromethanesulfonic anhydride (Tf 2 O) was slowly added dropwise under -78°C conditions. After the dropwise addition finished, stirring was conducted at -78°C for 30 minutes, and then the reaction solution was allowed to reach room temperature.
  • Tf 2 O trifluoromethanesulfonic anhydride
  • the reaction solution was cooled again to 0°C, and a saturated sodium hydrogen carbonate aqueous solution was slowly added until the pH reached approximately 7 to 8.
  • the solution was extracted with ethyl acetate 3 times, and the gathered organic layer was dried over sodium sulfate and then concentrated in a rotary evaporator.
  • the resultant crude product was purified by silica gel column chromatography (eluent: hexane) to result in 9.93 g (29.2 mmol, yield 67%) of the compound 23.
  • the obtained compound 23 exhibited a good agreement with the spectrum of the identical compound synthesized in " Angew. Chem. Int. Ed. 2011, 50, 5674-5677 ".
  • the 1 H-NMR data of the compound 23 obtained are shown below.
  • a compound 24 shown below was synthesized by a method mentioned below.
  • a 1 L 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a reflux condenser, a flat plug, and a three-way cock. Under a nitrogen atmosphere, 22.2 g (146 mmol, 5 equivalents) of cesium fluoride and 290 mL of acetonitrile were loaded thereto. Subsequently, 12.3 mL (146 mmol, 5 equivalents) of cyclopentadiene, obtained by pyrolysis of dicyclopentadiene immediately before, was added to the reaction solution. Immediately thereafter, 9.93 g (29.2 mmol, 1 equivalent) of the compound 23 was added thereto.
  • a compound 25 shown below was synthesized by a method mentioned below.
  • a 500 mL 3-neck flask including a magnetic stirring bar was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 120 mL of t BuOH, 35 mL of water, and 5.32 g (1 equivalent) of the mixed solution of the compound 24 obtained in ⁇ Synthesis of compound 24> were loaded thereto, and the reaction solution was cooled to 0°C. 1.45 g (36.2 mmol, 1.25 equivalents) of NaOH and 6.86 g (43.4 mmol, 1.5 equivalents) of KMnO 4 were dissolved in 130 mL of water, and the solution was slowly added dropwise to the reaction solution.
  • the 1 H-NMR data of the compound 25 obtained are shown below.
  • a compound 26 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 5.31 g (24.3 mmol, 1 equivalent) of the compound 25 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 7.0 mL (60.3 mmol, 2.5 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight. After the reaction finished, the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour.
  • the melting completion temperature of the compound 26 obtained was 114°C.
  • a compound 27 shown below was synthesized by a method mentioned below.
  • a compound 28 shown below was synthesized by a method mentioned below.
  • a compound 29 shown below was synthesized by a method mentioned below.
  • a 500 mL 3-neck flask including a magnetic stirring bar was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 70 mL of t BuOH, 20 mL of water, and 3.39 g (17 mmol, 1 equivalent) of the compound 28 contaminated with a small amount of hexane obtained in ⁇ Synthesis of compound 28> were loaded thereto, and the reaction solution was cooled to 0°C. 0.85 g (21.3 mmol, 1.25 equivalents) of NaOH and 4.03 g (25.5 mmol, 1.5 equivalents) of KMnO 4 were dissolved in 80 mL of water, and the solution was slowly added dropwise to the reaction solution.
  • a compound 30 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.19 g (11.5 mmol, 1 equivalent) of the compound 29 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 2.94 mL (25.3 mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted for 3 hours. After the reaction finished, the solution was cooled to 0°C, 20 mL of methanol was added, and stirring was conducted for an hour.
  • the melting completion temperature of the compound 30 obtained was 131°C.
  • a compound 31 shown below was synthesized by a method mentioned below.
  • a compound 32 shown below was synthesized by a method mentioned below.
  • a compound 33 shown below was synthesized by a method mentioned below.
  • a compound 34 shown below was synthesized by a method mentioned below.
  • a 500 mL 3-neck flask including a magnetic stirring bar was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 135 mL of t BuOH, 40 mL of water, and 5.58 g (32.8 mmol, 1 equivalent) of the compound 33 were loaded thereto, and the reaction solution was cooled to 0°C. 1.64 g (41.0 mmol, 1.25 equivalents) of NaOH and 7.78 g (49.2 mmol, 1.5 equivalents) of KMnO 4 were dissolved in 150 mL of water, and the solution was slowly added dropwise to the reaction solution.
  • a compound 35 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 5.29 g (25.9 mmol, 1 equivalent) of the compound 34 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 6.60 mL (57.0 mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted for 4 hours.
  • the solution was cooled to 0°C, 20 mL of methanol was added, and stirring was conducted for an hour. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the melting completion temperature of the compound 35 obtained was 138°C.
  • a compound 36 shown below was synthesized by a method mentioned below.
  • a 500 mL 3-neck flask including a magnetic stirring bar was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 110 mL of t BuOH, 35 mL of water, and 5.00 g (26.0 mmol, 1 equivalent) of 1,4-dihydro-1,4-methanoanthracene were loaded thereto, and the reaction solution was cooled to 0°C. 1.30 g (32.5 mmol, 1.25 equivalents) of NaOH and 6.16 g (39.0 mmol, 1.5 equivalents) of KMnO 4 were dissolved in 120 mL of water, and the solution was slowly added dropwise to the reaction solution.
  • a compound 37 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.57 g (11.4 mmol, 1 equivalent) of the compound 36 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 2.90 mL (25.1 mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight. After the reaction finished, the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour.
  • the 1 H-NMR data of the compound 37 obtained are shown below.
  • the melting completion temperature of the compound 37 obtained was 164°C.
  • a compound 38 shown below was synthesized by a method mentioned below.
  • a 500 mL 3-neck flask including a magnetic stirring bar was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 150 mL of t BuOH, 50 mL of water, and 4.33 g (30.0 mmol, 1 equivalent) of 1,4-epoxy-1,4-dihydronaphthalene were loaded thereto, and the reaction solution was cooled to 0°C. 1.50 g (37.5 mmol, 1.25 equivalents) of NaOH and 7.11 g (45.0 mmol, 1.5 equivalents) of KMnO 4 were dissolved in 150 mL of water, and the solution was slowly added dropwise to the reaction solution.
  • a compound 39 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 3.10 g (17.4 mmol, 1 equivalent) of the compound 38 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 4.50 mL (38.3 mmol, 2.2 equivalents) of benzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the melting completion temperature of the compound 39 obtained was 188°C.
  • a compound 40 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.13 g (12.1 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 3.42 mL (26.8 mmol, 2.2 equivalents) of o-toluoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for 30 minutes. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 40 obtained are shown below.
  • the melting completion temperature of the compound 40 obtained was 119°C.
  • a compound 41 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.15 g (12.2 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 3.54 mL (26.8 mmol, 2.2 equivalents) of m-toluoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for 30 minutes. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 41 obtained are shown below.
  • the melting completion temperature of the compound 41 obtained was 84°C.
  • a compound 42 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.23 g (12.6 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 4.20 mL (28.4 mmol, 2.3 equivalents) of 3,5-dimethylbenzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 42 obtained are shown below.
  • the melting completion temperature of the compound 42 obtained was 118°C.
  • a compound 43 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.26 g (12.8 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto. After the reaction solution was cooled to 0°C, 5.00 g (29.3 mmol, 2.3 equivalents) of 4-methoxybenzoyl chloride was slowly loaded. After the loading finished, the temperature was raised to room temperature, and stirring was conducted overnight. After the reaction finished, the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour.
  • the melting completion temperature of the compound 43 obtained was 167°C.
  • a compound 44 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.26 g (12.8 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 3.81 mL (27.9 mmol, 2.2 equivalents) of 3-methoxybenzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 44 obtained are shown below.
  • the melting completion temperature of the compound 44 obtained was 113°C.
  • a compound 45 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 1.78 g (10.1 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 3.30 mL (22.3 mmol, 2.2 equivalents) of 3-(trifluoromethyl)benzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 45 obtained are shown below.
  • the melting completion temperature of the compound 45 obtained was 124°C.
  • a compound 46 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.06 g (11.7 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 3.80 mL (25.3 mmol, 2.2 equivalents) of 1-naphthoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 46 obtained are shown below.
  • the melting completion temperature of the compound 46 obtained was 158°C.
  • a compound 47 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.03 g (11.5 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto. After the reaction solution was cooled to 0°C, 4.80 g (25.2 mmol, 2.2 equivalents) of 2-naphthoyl chloride was slowly loaded. After the loading finished, the temperature was raised to room temperature, and stirring was conducted overnight. After the reaction finished, about 10 mL of dichloromethane was added, and stirring was conducted for further 3 hours.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 47 obtained are shown below.
  • the melting completion temperature of the compound 47 obtained was 201°C.
  • a compound 48 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.15 g (12.2 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 4.00 mL (26.8 mmol, 2.2 equivalents) of 2-ethylbenzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the melting completion temperature of the compound 48 obtained was 52°C.
  • a compound 49 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.19 g (12.4 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 4.50 g (26.7 mmol, 2.2 equivalents) of 2,3-dimethylbenzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for an hour. After addition of about 20 mL of water and about 30 mL of dichloromethane, the solution was extracted with dichloromethane 3 times, and the gathered organic layer was washed with a saturated ammonium chloride aqueous solution twice. After drying over sodium sulfate, the solution was concentrated in a rotary evaporator.
  • the 1 H-NMR data of the compound 49 obtained are shown below.
  • the melting completion temperature of the compound 49 obtained was 107°C.
  • a compound 50 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 50 obtained was 252°C.
  • a compound 51 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.80 g (15.9 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 4.38 mL (32.3 mmol, 2 equivalents) of cyclohexanecarbonyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight.
  • the melting completion temperature of the compound 51 obtained was 80°C.
  • a compound 52 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 3.22 g (18.3 mmol, 1 equivalent) of the compound 5 and about 10 mL of pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 4.25 mL (40.3 mmol, 2.2 equivalents) of isobutyryl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight. After the reaction finished, the solution was cooled to 0°C, 20 mL of methanol was added, and stirring was conducted for 40 minutes.
  • a compound 53 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 54 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 55 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the melting completion temperature of the compound 55 obtained was 186°C.
  • a compound 56 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the melting completion temperature of the compound 56 obtained was 146°C.
  • a compound 57 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the melting completion temperature of the compound 57 obtained was 86°C.
  • a compound 58 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the melting completion temperature of the compound 58 obtained was 173°C.
  • a compound 59 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the reaction solution was concentrated under reduced pressure, 20 mL of a 2 mol/L sodium hydroxide aqueous solution, and 50 mL of ethyl acetate were added at 50°C or less thereto, and stirring was conducted at 50°C for an hour.
  • the organic layer was fractionated, and the water layer was extracted with ethyl acetate 3 times.
  • the organic layer was washed with brine, dried over sodium sulfate, and then concentrated in a rotary evaporator.
  • the compound 59 was continuously allowed to react without purification.
  • a compound 60 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the melting completion temperature of the compound 60 obtained was 125°C.
  • a compound 61 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the reaction solution was concentrated under reduced pressure, 20 mL of a 2 mol/L sodium hydroxide aqueous solution, and 50 mL of ethyl acetate were added thereto at 50°C or less, and stirring was conducted at 50°C for an hour.
  • the organic layer was fractionated, and the water layer was extracted with ethyl acetate 3 times.
  • the organic layer was washed with brine, dried over sodium sulfate, and then concentrated in a rotary evaporator.
  • the compound 61 was continuously allowed to react without purification.
  • a compound 62 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the melting completion temperature of the compound 62 obtained was 192°C.
  • a compound 63 shown below was synthesized by a method mentioned below.
  • the organic layer was separated and washed with water and brine in the order mentioned. After the organic layer was dried over magnesium sulfate, the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator to thereby give 15.42 g of a crude product.
  • the crude product was purified by silica gel column chromatography to give 4.9 g of the compound 63 as a mixture with impurities.
  • a compound 64 shown below was synthesized by a method mentioned below.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the reaction solution until a white precipitate was formed.
  • the precipitate formed was removed by filtration, and the filtrate was extracted with ethyl acetate 4 times.
  • the organic layer was washed with brine and dried over magnesium sulfate.
  • the magnesium sulfate was filtered off, and the obtained organic layer was concentrated in a rotary evaporator.
  • the crude product was purified by silica gel column chromatography to give 0.72 g of the compound 64 as an isomer mixture.
  • the magnesium sulfate was filtered, and the filtrate was concentrated in a rotary evaporator to thereby give a crude product.
  • the crude product was purified by silica gel column chromatography to give 0.41 g (white solid) of the compound 65-1 and 0.53 g (white solid) of the compound 65-2.
  • the stereostructures of the compounds 65-1 and 65-2 were determined by NOESY.
  • the 1 H-NMR data of the compound 65-1 and compound 65-2 are shown below.
  • the melting completion temperature of the compound 65-1 obtained was 143°C.
  • the melting completion temperature of the compound 65-2 obtained was 193°C.
  • a compound 66 shown below was synthesized by a method mentioned below.
  • a compound 67 shown below was synthesized by a method mentioned below.
  • a compound 68 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 68 obtained was 174°C.
  • a compound 69 shown below was synthesized by a method mentioned below.
  • a compound 70 shown below was synthesized by a method mentioned below.
  • a compound 71 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 71 obtained was 173°C.
  • a compound 72 shown below was synthesized by a method mentioned below.
  • a compound 73 shown below was synthesized by a method mentioned below.
  • a compound 74 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 74 obtained was 218°C.
  • a compound 75 shown below was synthesized by a method mentioned below.
  • a compound 76 shown below was synthesized by a method mentioned below.
  • a compound 77 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 77 obtained was 175°C.
  • a compound 78 shown below was synthesized by a method mentioned below.
  • a compound 79 shown below was synthesized by a method mentioned below.
  • a compound 80 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 80 obtained was 184°C.
  • a compound 81 shown below was synthesized by a method mentioned below.
  • a compound 82 shown below was synthesized by a method mentioned below.
  • a compound 83 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 83 obtained was 176°C.
  • a compound 84 shown below was synthesized by a method mentioned below.
  • a compound 85 shown below was synthesized by a method mentioned below.
  • a compound 86 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 86 obtained was 227°C.
  • a compound 87 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 87 obtained was 220°C.
  • a compound 88 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 88 obtained was 158°C.
  • a compound 89 shown below was synthesized by a method mentioned below.
  • the product gathered by filtration was washed with hexane and then dissolved in 100 mL of dichloromethane.
  • the solution was washed twice with 100 mL of 1 N hydrochloric acid and once each with 100 mL of a saturated sodium hydrogen carbonate aqueous solution and 100 mL of brine in the order mentioned.
  • the obtained organic layer was dried over magnesium sulfate.
  • the resulting solid was dissolved again in 30 mL of chloroform, and the solution was added dropwise to 150 mL of methanol to give a solid.
  • the melting completion temperature of the compound 89 obtained was 221°C.
  • a compound 90 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 90 obtained was 178°C.
  • a compound 91 shown below was synthesized by a method mentioned below.
  • a 300 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 3.08 g (18.8 mmol) of 3-isopropylbenzoic acid, 60 mL of dichloromethane, and 2 drops of DMF were added thereto. After the reaction solution was cooled to 0°C, 2.57 mL (30 mmol) of oxalyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted at room temperature for 3 hours. The volatile compound in the reaction system was removed under reduced pressure to give the compound 91. The compound was used in ⁇ Synthesis of compound 92> without further purification.
  • a compound 92 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 1.6 g of the compound 5 and 10 mL of dehydrated pyridine were added thereto. After the reaction solution was cooled to 0°C, 20 mL of a dichloromethane solution of the compound 91 synthesized in ⁇ Synthesis of compound 91> was slowly added to a pyridine solution of the compound 5, and stirring was conducted overnight. After the reaction finished, the solution was cooled to 0°C, 20 mL of methanol was added thereto, and stirring was conducted for an hour.
  • the melting completion temperature of the compound 92 obtained was 93°C.
  • a compound 93 shown below was synthesized by a method mentioned below.
  • a compound 93 was synthesized in accordance with the operation and equivalence relationship described in ⁇ Synthesis of compound 91> except that 4.21 g (28.0 mmol) of 3,4-dimethylbenzoic acid was used instead of using 3-isopropylbenzoic acid in ⁇ Synthesis of compound 91>.
  • the compound 93 obtained was used as was in ⁇ Synthesis of compound 94>.
  • a compound 94 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.13 g (12.1 mmol) of the compound 5 and 10 mL of dehydrated pyridine were added thereto. After the reaction solution was cooled to 0°C, 20 mL of a dichloromethane solution of the compound 93 synthesized in ⁇ Synthesis of compound 93> was slowly added to a pyridine solution of the compound 5, and stirring was conducted overnight. After the reaction finished, the solution was cooled to 0°C, 20 mL of methanol was added thereto, and stirring was conducted for an hour.
  • the melting completion temperature of the compound 94 obtained was 158°C.
  • a compound 95 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 96 shown below was synthesized by a method mentioned below.
  • a 500 mL 3-neck flask including a magnetic stirring bar was equipped with a dropping funnel, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 60 mL of a mixed solution of tert-butyl alcohol and acetone, 20 mL of water, and 2.51 g (11.4 mmol) of the compound 95 were added thereto, and the reaction solution was cooled to 0°C. 0.57 g (14.3 mmol) of sodium hydroxide and 2.70 g (17.1 mmol) of potassium permanganate were dissolved in 60 mL of water, and this solution was slowly added dropwise to the reaction solution prepared previously.
  • a compound 97 shown below was synthesized by a method mentioned below.
  • a 100 mL 3-neck flask including a magnetic stirring bar sufficiently dried by heating was equipped with a flat plug, a thermometer, and a three-way cock. Under a nitrogen atmosphere, 2.18 g (8.6 mmol) of the compound 96 and 10 mL of dehydrated pyridine were added thereto, and the flat plug was replaced with a dropping funnel. After the reaction solution was cooled to 0°C, 2.20 mL (18.9 mmol) of benzoyl chloride was slowly added dropwise. After the dropwise addition finished, the temperature was raised to room temperature, and stirring was conducted overnight. After the reaction finished, the solution was cooled to 0°C, 10 mL of methanol was added, and stirring was conducted for 30 minutes.
  • the melting completion temperature of the compound 97 obtained was 158°C.
  • a compound 98 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the resultant crude product was combined with a resultant crude product using 5.0 g of p-benzoquinone in accordance with the similar operation and equivalence relationship (41.87 g in total), and the combined crude products were purified by silica gel column chromatography to give 30.0 g of the compound 98.
  • a compound 99 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 100 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 102 shown below was synthesized by a method mentioned below.
  • a compound 103 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 103 obtained was 149°C.
  • a compound 104 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 105 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • NMO 4-methylmorpholine N-oxide
  • the filtrate was collected by filtration under reduced pressure, and the pH of the filtrate was adjusted to 7 using 1 N sulfuric acid.
  • the organic solvent was removed from the filtrate under reduced pressure at an external temperature of 40°C, and the pH of the remaining aqueous solution was adjusted to 3 again with 1 N sulfuric acid.
  • Excess sodium chloride and 500 mL of ethyl acetate were added and stirred, the solution was filtered under reduced pressure, and undissolved sodium chloride was filtered off.
  • the solution was liquid-separated into an organic layer and a water layer, and the collected water layer was extracted 3 times with 400 mL of ethyl acetate.
  • the organic layer was gathered, dried over sodium sulfate, and filtered.
  • a compound 106 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 106 obtained was 127°C.
  • a compound 107 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 108 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • the organic layer was separated, added to 500 mL of 10% hydrochloric acid cooled with an ice bath, and stirred. Subsequently, the organic layer was separated, added to 500 mL of a saturated sodium hydrogen carbonate aqueous solution, and stirred. The organic layer was separated again and subjected to liquid-separation and washing with 500 mL of brine. The organic layer was dried over sodium sulfate and filtered. Then, the filtrate was concentrated in a rotary evaporator, and the concentrate was vacuum-dried at an external temperature of 40°C for 2 hours to result in 70.4 g (yield 97%) of the compound 108.
  • a compound 109 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 110 shown below was synthesized by a method mentioned below.
  • a compound 111 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 111 obtained was 97°C.
  • a compound 112 shown below was synthesized by a method mentioned below according to the following reaction formula.
  • a compound 113 shown below was synthesized by a method mentioned below.
  • the filtrate was collected by filtration under reduced pressure, and the pH of the filtrate was adjusted to 7 using 1 N sulfuric acid.
  • the organic solvent was removed from the filtrate under reduced pressure at an external temperature of 40°C, and the pH of the remaining aqueous solution was adjusted to 3 again with 1 N sulfuric acid.
  • Excess sodium chloride and 600 mL of ethyl acetate were added and stirred, the solution was filtered under reduced pressure, and undissolved sodium chloride was filtered off.
  • the solution was liquid-separated into an organic layer and a water layer, and the collected water layer was extracted 3 times with 600 mL of ethyl acetate.
  • the organic layer was gathered, dried over sodium sulfate, and filtered.
  • a compound 114 shown below was synthesized by a method mentioned below.
  • the melting completion temperature of the compound 114 obtained was 122°C.
  • a compound 115 shown below was synthesized by a method mentioned below.
  • a compound 116 shown below was synthesized by a method mentioned below.
  • a solid titanium catalyst component [ ⁇ 1] prepared by the procedure above was preserved as a decane slurry, and a portion thereof was dried in order to examine the catalyst composition.
  • the composition of the solid titanium catalyst component [ ⁇ 1] thus obtained included 0.28% by mass titanium, 1.7% by mass magnesium, and 0.12% by mass 2-ethylhexyl alcohol residues.
  • the final melting point (Tmf) of the polymer in the present invention was measured by a differential scanning calorimeter (DSC) in a DSC220C apparatus manufactured by Seiko Instruments Inc. 3 to 10 mg of a specimen was sealed in an aluminum pan and heated from room temperature to 240°C at 80°C/minute. The specimen was retained at 240°C for 1 minute and then cooled to 0°C at 80°C/minute. After retained at 0°C for 1 minute, the specimen was heated to 150°C at 80°C/minute and retained for 5 minutes.
  • DSC differential scanning calorimeter
  • the specimen was heated to 180°C at 1.35°C/minute, and the intersection of the tangent of the inflection point on the high-temperature side of the peak provided in this final heating test and the base line was employed as the final melting point (Tmf).
  • Tmf can be considered one parameter for evaluating the ease of crystallization and the crystal structure, for example, of a polymer in the ultra-high molecular weight region, which is said to tend to be difficult to crystallize. More specifically, it can be considered that, as this Tmf value is higher, the ultra-high molecular weight polymer component is more likely to form crystals that is strong and has high heat resistance.
  • the thick line represents the near side of the paper plane
  • the dotted line represents the far side of the paper plane
  • the compound 201 corresponds to diol compound derived from the endo form shown in the formula (34) above.
  • the thick line represents the near side of the paper plane, and the compound 202 corresponds to diol compound derived from the exo form shown in the formula (34) above.
  • a 2-liter flask was equipped with a mechanical stirrer and purged with nitrogen by allowing nitrogen to flow inside.
  • 25.4 g of an olefin ((a compound in which, in the formula (33), R 4 , R 9 , and R 31 to R 34 are hydrogen atoms, and X is CH 2 ), 440 ml of tert-butyl alcohol, and 110 ml of water were added into the flask, and the internal temperature was cooled to 0°C.
  • To another 1 L beaker 30 g of potassium permanganate, 600 ml of water, and 6.60 g of sodium hydroxide were added to prepare a potassium permanganate alkali aqueous solution.
  • the 2-liter flask was equipped with a dropping funnel, and the potassium permanganate alkali aqueous solution prepared was loaded to the dropping funnel.
  • the potassium permanganate alkali aqueous solution was slowly added dropwise such that the internal temperature did not exceed 5°C.
  • stirring was conducted at an internal temperature of 0°C for an hour.
  • a saturated sodium metabisulfite aqueous solution was prepared and slowly added dropwise to the previous reaction solution until a white precipitate was formed. After the dropwise addition, the temperature was raised to room temperature to cause a white solid to precipitate. The supernatant organic layer was collected, and then an operation of extraction from the water layer with ethyl acetate was conducted twice.
  • the melting completion temperature of the compound 203 was 108.7°C.
  • the melting completion temperature of the compound 204 was 168.2°C.
  • the melting completion temperature of the compound 205 was 116.0°C.
  • the melting completion temperature of the compound 209 was 149.8°C.
  • the melting completion temperature of the compound 210 was 173.8°C.
  • the melting completion temperature of the compound 211 was 124.3°C.
  • the melting completion temperature of the compound 213 was 127.7°C.
  • the compound 215 exhibits behavior of gradually melting from 62.5°C.
  • the melting completion temperature of the compound 216 was 139.4°C.
  • the melting completion temperature of the compound 217 was 208.2°C.
  • Synthesis of the compound 218 was conducted in accordance with the operation and equivalence relationship described in ⁇ Synthesis of compound 214> except that 4.63 g (1 equivalent) of 3,4-dimethylbenzoic acid was used instead of using 3-phenylbenzoic acid in ⁇ Synthesis of compound 214>.
  • the compound 218 obtained was used as was in Synthesis of compound 219.
  • the melting completion temperature of the compound 219 was 131.1°C.
  • the compound 220 was synthesized in accordance with the operation and equivalence relationship described in ⁇ Synthesis of compound 214> except that 4.85 g (1 equivalent) of 5,6,7,8-tetrahydro-2-naphthoic acid was used instead of using 3-phenylbenzoic acid in ⁇ Synthesis of compound 214>.
  • the compound 220 obtained was used as was in Synthesis of compound 221.
  • the melting completion temperature of the compound 221 was 151.2°C.
  • the compound 222 was synthesized in accordance with the operation and equivalence relationship described in ⁇ Synthesis of compound 214> except that 5.0 g (1 equivalent) of 4-methoxy-3-methylbenzoic acid was used instead of using 3-phenylbenzoic acid in ⁇ Synthesis of compound 214>.
  • the compound 222 obtained was used as was in Synthesis of compound 223.
  • the melting completion temperature of the compound 223 was 187.1°C.
  • the novel ester compound according to the present invention is a compound useful for production of resin additives, cosmetics and external preparations for skin, microbicidal compositions, antioxidants, chelators, and Ziegler-Natta catalysts.
  • the compound can be utilized particularly as a catalyst component for Ziegler-Natta catalysts.
  • the compound enables production of a catalyst that offers excellent stereoregularity and productivity on polymerization of polypropylene, and thus has a significantly high industrial value.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pyrane Compounds (AREA)
EP21861653.0A 2020-08-26 2021-08-26 Ester compound Pending EP4206182A1 (en)

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PCT/JP2021/031281 WO2022045231A1 (ja) 2020-08-26 2021-08-26 エステル化合物

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IT1292109B1 (it) 1997-06-09 1999-01-25 Montell North America Inc Componenti e catalizzatori per la polimerizzazione di olefine
JP4717219B2 (ja) 1999-04-15 2011-07-06 バセル テクノロジー カンパニー ビー．ブイ． オレフィン重合用の成分および触媒
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CN1169845C (zh) 2002-02-07 2004-10-06 中国石油化工股份有限公司 用于烯烃聚合的固体催化剂组分和含该催化剂组分的催化剂及其应用
JP4980670B2 (ja) 2006-08-01 2012-07-18 三井化学株式会社 環状オレフィンおよびその製法
JP5248322B2 (ja) 2006-11-20 2013-07-31 三井化学株式会社 環状オレフィンの製造方法
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JP4974732B2 (ja) 2007-03-30 2012-07-11 三井化学株式会社 環状オレフィンの製造方法
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JP7109178B2 (ja) 2016-11-29 2022-07-29 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法、並びに、化合物及び酸発生剤

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BR112023003400A2 (pt) 2023-04-11

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